The present work describes the Li-ion conduction in Poly(vinyl acetate) (PVAc) based polymer blend electrolytes have been synthesized by solvent casting technique for lithium battery applications. Characterization by XRD, SEM, AFM, FTIR, TG/DTA and photoluminescence was performed for synthesized polymer electrolytes. The thermal behaviour of the samples was ascertained from differential scanning calorimeter (DSC) and TG/DTA. The temperature dependence of conductivity of the polymer electrolytes was measured and the maximum ionic conductivity of 0.5269 x 10(-4) Scm(-1) at 303 K for PVAc:PVdF-co-HFP ((25/75)wt%):LiClO(4) (8 wt%) complex. Surface morphology was examined from various surface scanning techniques such as scanning electron microscope (SEM) and atomic force microscope (AFM). Photoluminescence measurements demonstrated that the PVAc based polymer blend electrolyte shows minimum intensity and the results are detailed in this paper. (C) 2011 Elsevier B.V. All rights reserved.